EP0030434A1 - Methanol homologation using cobalt-ruthenium catalysts - Google Patents
Methanol homologation using cobalt-ruthenium catalysts Download PDFInfo
- Publication number
- EP0030434A1 EP0030434A1 EP19800304289 EP80304289A EP0030434A1 EP 0030434 A1 EP0030434 A1 EP 0030434A1 EP 19800304289 EP19800304289 EP 19800304289 EP 80304289 A EP80304289 A EP 80304289A EP 0030434 A1 EP0030434 A1 EP 0030434A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- methanol
- component
- cobalt
- ruthenium
- ethanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- This invention relates to a homogeneous process for the homologation of methanol to acetaldehyde, ethanol or mixtures thereof.
- methanol is reacted with carbon monoxide and hydrogen in the presence of a catalytic system containing cobalt and ruthenium.
- U.S. Patent No. 4,133,966 (Pretzer et al) relates to a process for selectively preparing ethanol from methanol, hydrogen and carbon monoxide in the presence of a catalytic system containing cobalt acetylacetonate, an iodine compound as a first promoter, a ruthenium compound as a second promoter and a tertiary organo Group VA compound.
- a catalytic system containing cobalt acetylacetonate, an iodine compound as a first promoter, a ruthenium compound as a second promoter and a tertiary organo Group VA compound.
- cobalt-acetylacetonate as the cobalt source. If selectivity to acetaldehyde is desired, U.S. Patent No.
- the selective conversion of methanol to acetaldehyde, ethanol or mixtures thereof is accomplished by the use of a catalytic system containing cobalt-ruthenium complexes or mixtures of specific cobalt compounds with ruthenium compounds.
- the present process for the homogeneous conversion of methanol to acetaldehyde, ethanol or mixtures thereof comprises contacting methanol with carbon monoxide and hydrogen in a CO:H 2 ratio of from 1:10 to 10:1 at a temperature of from about 100 to 300°C and a pressure of from about 2 to 100 MPa in the presence of a catalytically effective amount of a catalyst system, said catalyst system consisting essentially of (a) a cobalt-ruthenium complexe selected from HCORu 3 (CO) 13 , and MLC O Ru 3 (CO) 13J wherein M is a cation, or a soluble ruthenium compound plus Co 2 (CO) 8-n (PR 3 ) n where n is from 0 to 4 and each R is independently C l to C 20 aliphatic radical, C 6 to C 10 aryl, aralkyl having from 1 to 6 carbon atoms in the alkyl or C 3 to C 8 cycloalkyl; (b) i
- the homogeneous catalytic system of the invention provides a highly selective method of producing ethanol or acetyldehyde by the homologation of methanol.
- the present process can achieve methanol conversions to ethanol of about 50 to 60% with only small amounts of by-products such as methyl ethyl ether, diethyl ether, propanol and ethyl acetate.
- the attainable selectivity to ethanol is about 80% and the total selectivity to acetaldehyde plus ethanol is about 93%.
- M is a cation such as alkali metal, NR 1 R 2 R 3 R 4 ⁇ , PR 1 R 2 R 3 R 4 ⁇ or ⁇ 3 PNP ⁇ 3 ⁇
- R 1 to R 4 are independently hydrogen, C 1 to C 20 alkyl, C 3 to C 8 cycloalkyl, benzyl, phenyl or phenyl substituted by C 1 to C 6 alkyl, C 1 to C 6 alkoxy or halogen, almost no compounds containing cobalt and ruthenium are known.
- a novel compound containing a cyclopentadienide (Cp) ligand can be prepared by a displacement reaction between C P Ru(P ⁇ 3 ) 2 Cl and TlCo(CO) 4 in tetrahydrofuran.
- the reaction is generally and specifically illustrated as follows: where R 6 is C 1 to C 6 alkyl, L is independently PR 3 , CO or P(OR) 3 where R is defined above; X is halogen, p is a number from 0 to 5 and m is a number from 0 to 3.
- Co 2 CO 8 or phosphine derivatives thereof plus a soluble ruthenium compound as a component in the catalyst system.
- the ratio of Co to Ru may range from 0.1:1 to 10:1.
- the preparation of Co 2 (CO) 8 is well-known and compounds of the general formula Co 2 CO 8-n (PR 3 ) n are prepared by ligand exchange reactions between Co 2 (CO) 8 and PR 3 .
- Suitable ruthenium compounds are those which are soluble in the reaction medium.
- Preferred ruthenium compounds include CpRu(P ⁇ 3 ) 2 Cl, Ru(acetylacetonate) 3 , Ru(acetylacetonate)(CO) 2 , RU(CO) 3 (P 3 ) 2 and Ru 3 (CO) 12 .
- the concentration of total cobalt and ruthenium may range from 1 ⁇ 10 -5 to 1 ⁇ 10 -1 M, preferably 1 ⁇ 10 -4 to 1 ⁇ 10 -2 M. Higher concentrations are technically feasible but provide no particular advantage.
- the preferred temperature range is from 140 to 230°C, most preferably from 170 to 220°C.
- acetaldehyde formation is favored by a lower temperature range of from 140 to 200°C whereas the preferred range for ethanol is from 200 to 225°C.
- the preferred pressure is from 10 to 80 MPa, especially 15 to 60 MPa (1 MPa ⁇ 10 atm). Pressures higher than 100 MPa are possible but usually require special equipment which is economically disadvantageous. It is most preferred to operate at as high a pressure as is technically or economically feasible.
- the homologation reaction is promoted by iodine or iodides.
- Suitable iodides promoters include HI, alkali metal iodide, R 1 R 2 R 3 R 4 N ⁇ I ⁇ or R 1 R 2 R 3 R 4 ⁇ I ⁇ where R 1 to R 4 are defined as hereinbefore.
- Preferred promoters are HI or CH 3 I.
- the amounts of iodide as measured by the I:M ratio, i.e., the number of moles of iodide to total gram atoms of metal present (Co + Ru), is from 0.2:1 to 100:1, preferable from 0.5:1 to 4:1.
- phosphines have the formula PR 3 or P(OR) 3 where R is preferably alkyl of 1 to 10 carbon atoms, cycloalkyl of 5 to 7 carbon atoms, phenyl, tolyl or benzyl.
- the phosphine may be a ligand on either the cobalt or ruthenium metal atom or may be added separately to the reaction mixture.
- reaction times can vary from about 0.1 to 24 hours. If acetaldehyde is the desired product, reaction periods of from 0.5 to 3 hours are preferred, whereas the preferred reaction times for ethanol are from 3 to 10 hours.
- the homologation reaction is conducted in a solvent. Since methanol is a reactant, it is the preferred solvent. While other organic solvents,.which are inert under reaction.conditions, may be employed, e.g, ethers and aromatics, they provide no advantage over methanol and require an additional separation step.
- the reactor is pressurized with CO and H 2 at a H 2 :CO ratio of from 10:1 to 1:10, preferably 5:1 to 1:5. If acetaldehyde is the desired product, then a H 2 :CO range of from 0.5:1 to 1:1 is preferred. Excess hydrogen favors the formation of ethanol and the preferred H 2 :CO ratio is from 1.3:1 to 3:1.
- the process may be conducted in a batchwise or continuous manner in a conventional high pressure reactor having heating and agitation means.
- the reactor is charged with methanol containing dissolved metal (Ru + Co) compound, flushed with CO and pressurized with the desired CO/H 2 mixture.
- the reactor is heated with agitation and the pressure adjusted using the CO/H 2 mixture.
- the products are isolated using conventional techniques such as distillation.
- the first product formed in the homologation of methanol is probably acetaldehyde, which is formed from the reduction of a catalytic intermediate into which CO has been inserted.
- Acetaldehyde can react with methanol to form an acetal but the acetal will react with water to regenerate acetaldehyde.
- Acetaldehyde is a reactive species and can be further reduced to ethanol.
- ethanol is much less reactive to homologation than is methanol.
- Preferred conditions for acetaldehyde formation are temperatures of from 140 to 200°C, an H 2 :CO ratio from about 0.5:1 to 1:1 and reaction times of from 1 to 3 hours, whereas preferred ethanol reaction conditions are temperatures of from 200 to 220°C, H 2 :CO ratios of from 1.3 to 1 to 3:1 and reaction times of from 3 to 10 hours.
- the very high selectivities achievable for ethanol indicates that ethanol formation can be achieved without substantial by-product formation.
- HRuCo3(CO)12 and its salts are prepared according to methods described in J. Chem. Soc. (A):1444 (1968).
- CpRu(P ⁇ 3 ) 2 Co(CO) 4 is described as follows.
- TlCo(CO) 4 and CpRu(P ⁇ 3 ) 2 Cl were prepared by known methods (J. Organomet. Chem., 43:C44 (1972); Aust. J. Chem., 30:1601 (1977)).
- a mixture of 1.88 g (5 mmoles) TlCo(CO) 4 and 3.63 g (5 mmoles) CpRu(P ⁇ 3 ) 2 Cl in 75 ml THF was refluxed for 18 hours under nitrogen.
- the cooled solution was filtered to remove the T1C1 which precipitated (1.16 g) and the deep colored filtrate was added to 200 ml pentane and the solution chilled to -20°C overnight.
- the deep purple crystals which formed were collected on a filter and dried under nitrogen. Yield 1.2 g (28%).
- reaction temperature 220°C
- H 2 :C0 1.5
- pressure 27 MPa
- CH 3 I: metal 2
- the reaction was carried out as follows.
- the high pressure reaction (27 MPa) was carried out in an Autoclave Engineers 1 liter stirred autoclave which was equipped with a catalyst blowcase and which was directly fed by high pressure syn-gas lines.
- the auto- calve was charged with 250 ml methanol with 50 ml toluene as an internal standard and the appropriate amount of methyl iodide, and preheated to the reaction temperature.
- the catalyst dissolved in 100 ml methanol was then introduced through the blowcase and the pressure immediately brought to the desired level. Liquid samples were taken at desired intervals during the reaction and a gas sample was taken at the conclusion of the reaction.
- Example 2 This example is directed to a comparison of Co complexes, Ru complexes and mixtures thereof versus the preformed Ru-Co complex with respect to the homologation reaction.
- Example 2 was repeated except that the active metal of the catalyst system was varied. Table II summarizes the results.
- Fig. 1 illustrates ethanol product selectivity as a function of reaction time. The figure indicates that at 220°C, maximum selectivity to ethanol occurs at from about 3 to 6 hours.
- Example 2 The effect of temperature, phosphine ligand and metal is illustrated in this example.
- the procedure of Example 2 was followed except that the residence time was 3 hours and the nature of the metal component of the catalyst system was varied.
- the data are shown in Table III.
- CH 3 I was substituted for I 2 as a promoter.
- I 2 is used at the higher temperatures, no significant improvement in conversion occurs and CH 4 becomes a significant im p uritv forming in amounts of about 5-10% based on the reacted methanol.
- CH 3 1 increases methanol conversion but also results in increased acetaldehyde formation and decreased ethanol formation.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
- This invention relates to a homogeneous process for the homologation of methanol to acetaldehyde, ethanol or mixtures thereof. In one aspect of the invention, methanol is reacted with carbon monoxide and hydrogen in the presence of a catalytic system containing cobalt and ruthenium.
- The production of ethanol from methanol, carbon monoxide and hydrogen in the presence of a cobalt catalyst and an iodine promoter and a ruthenium halide or osmium halide secondary promoter is disclosed in U.S. Patent No. 3,285,948 (Butter). A similar catalyst system based oh C02(CO)8 is described by Metlin et al., Abstracts of Papers, 17th Spring Symposium of the Pittsburgh Catalysis Society, April, 1978.
- U.S. Patent No. 4,133,966 (Pretzer et al) relates to a process for selectively preparing ethanol from methanol, hydrogen and carbon monoxide in the presence of a catalytic system containing cobalt acetylacetonate, an iodine compound as a first promoter, a ruthenium compound as a second promoter and a tertiary organo Group VA compound. In order to avoid a wide variety of other products and optimize the formation of ethanol, patentees specify cobalt-acetylacetonate as the cobalt source. If selectivity to acetaldehyde is desired, U.S. Patent No. 4,151,208 (Pretzer et al) teaches a process wherein methanol, hydrogen and carbon monoxide are contacted with cobalt (II) meso-tetraaromaticporphine and an iodine promoter.
- It would be desirable to have a single catalyst system which can efficiently convert methanol to acetaldehyde or ethanol with a high degree of selectivity and without the formation of substantial amounts of undesirable by-products.
- According to this invention, the selective conversion of methanol to acetaldehyde, ethanol or mixtures thereof is accomplished by the use of a catalytic system containing cobalt-ruthenium complexes or mixtures of specific cobalt compounds with ruthenium compounds. The present process for the homogeneous conversion of methanol to acetaldehyde, ethanol or mixtures thereof comprises contacting methanol with carbon monoxide and hydrogen in a CO:H2 ratio of from 1:10 to 10:1 at a temperature of from about 100 to 300°C and a pressure of from about 2 to 100 MPa in the presence of a catalytically effective amount of a catalyst system, said catalyst system consisting essentially of (a) a cobalt-ruthenium complexe selected from
- The homogeneous catalytic system of the invention provides a highly selective method of producing ethanol or acetyldehyde by the homologation of methanol. The present process can achieve methanol conversions to ethanol of about 50 to 60% with only small amounts of by-products such as methyl ethyl ether, diethyl ether, propanol and ethyl acetate. The attainable selectivity to ethanol is about 80% and the total selectivity to acetaldehyde plus ethanol is about 93%. These are significantly higher selectivities compared to prior art processes, especially those producing ethanol or acetaldehyde using heterogeneous catalysts and the Fischer-Tropsch reaction.
- With the exception of HRuCo3(CO)12, MRuCo3(CO)12, HCoRu3CO13 and M[CoRu3(CO)13] where M is a cation such as alkali metal, NR1R2R3R4⊕, PR1R2R3R4⊕ or Ø3PNPØ3⊕ where R1 to R4 are independently hydrogen, C1 to C20 alkyl, C3 to C8 cycloalkyl, benzyl, phenyl or phenyl substituted by C1 to C6 alkyl, C1 to C6 alkoxy or halogen, almost no compounds containing cobalt and ruthenium are known. A novel compound containing a cyclopentadienide (Cp) ligand can be prepared by a displacement reaction between CPRu(PØ3)2Cl and TlCo(CO)4 in tetrahydrofuran. The reaction is generally and specifically illustrated as follows:
- As an alternative to employing a pre-formed cobalt-ruthenium complex, it is possible to use Co2CO8 or phosphine derivatives thereof plus a soluble ruthenium compound as a component in the catalyst system. The ratio of Co to Ru may range from 0.1:1 to 10:1. The preparation of Co2(CO)8 is well-known and compounds of the general formula Co2CO8-n(PR3)n are prepared by ligand exchange reactions between Co2(CO)8 and PR3. Suitable ruthenium compounds are those which are soluble in the reaction medium. Preferred ruthenium compounds include CpRu(PØ3)2Cl, Ru(acetylacetonate)3, Ru(acetylacetonate)(CO)2, RU(CO)3 (P3)2 and Ru3 (CO)12.
- When C02(CO)S is dissolved in methanol, a rapid disproportionation takes place, i.e.,
- While not wishing to be bound by a theoretical or mechanistic discussion, it appears likely that the active catalytic species existing under reaction conditions are derivatives of the present cobalt-ruthenium complexes or mixtures of Co2 (CO)8 or Co2 (CO)8-n (PR3)n plus Ru compound. This appears particularly likely in view of known Co and Ru ligand exchange reactions involving CO and PR3..If this is correct, then the starting compounds function as catalyst precursors.
- The concentration of total cobalt and ruthenium may range from 1×10-5 to 1×10-1M, preferably 1×10-4 to 1×10-2M. Higher concentrations are technically feasible but provide no particular advantage.
- The preferred temperature range is from 140 to 230°C, most preferably from 170 to 220°C. Generally, acetaldehyde formation is favored by a lower temperature range of from 140 to 200°C whereas the preferred range for ethanol is from 200 to 225°C.
- The preferred pressure is from 10 to 80 MPa, especially 15 to 60 MPa (1 MPa ≅ 10 atm). Pressures higher than 100 MPa are possible but usually require special equipment which is economically disadvantageous. It is most preferred to operate at as high a pressure as is technically or economically feasible.
- The homologation reaction is promoted by iodine or iodides. Suitable iodides promoters include HI, alkali metal iodide, R1R2R3R4N⊕I⊖ or R1R2R3R4⊕I⊖ where R1 to R4 are defined as hereinbefore. Preferred promoters are HI or CH3I. The amounts of iodide as measured by the I:M ratio, i.e., the number of moles of iodide to total gram atoms of metal present (Co + Ru), is from 0.2:1 to 100:1, preferable from 0.5:1 to 4:1.
- The presence of phosphines in the reaction mixture is important in achieving high methanol conversions. Preferred phosphines have the formula PR3 or P(OR)3 where R is preferably alkyl of 1 to 10 carbon atoms, cycloalkyl of 5 to 7 carbon atoms, phenyl, tolyl or benzyl. The phosphine may be a ligand on either the cobalt or ruthenium metal atom or may be added separately to the reaction mixture.
- The reaction times can vary from about 0.1 to 24 hours. If acetaldehyde is the desired product, reaction periods of from 0.5 to 3 hours are preferred, whereas the preferred reaction times for ethanol are from 3 to 10 hours.
- The homologation reaction is conducted in a solvent. Since methanol is a reactant, it is the preferred solvent. While other organic solvents,.which are inert under reaction.conditions, may be employed, e.g, ethers and aromatics, they provide no advantage over methanol and require an additional separation step.
- The reactor is pressurized with CO and H2 at a H2:CO ratio of from 10:1 to 1:10, preferably 5:1 to 1:5. If acetaldehyde is the desired product, then a H2:CO range of from 0.5:1 to 1:1 is preferred. Excess hydrogen favors the formation of ethanol and the preferred H2:CO ratio is from 1.3:1 to 3:1.
- The process may be conducted in a batchwise or continuous manner in a conventional high pressure reactor having heating and agitation means. In general, the reactor is charged with methanol containing dissolved metal (Ru + Co) compound, flushed with CO and pressurized with the desired CO/H2 mixture. The reactor is heated with agitation and the pressure adjusted using the CO/H2 mixture. After the reaction is completed, the products are isolated using conventional techniques such as distillation.
- While not wishing to limit the invention to any particular reaction mechanism, the above conditions with respect to reaction parameters may be explained as follows. The first product formed in the homologation of methanol is probably acetaldehyde, which is formed from the reduction of a catalytic intermediate into which CO has been inserted. Acetaldehyde can react with methanol to form an acetal but the acetal will react with water to regenerate acetaldehyde. Acetaldehyde is a reactive species and can be further reduced to ethanol. On the other hand, it is known that ethanol is much less reactive to homologation than is methanol.
- Since the reduction of acetaldehyde is the more difficult reaction, it can be seen that if high selectivity to acetaldehyde is desired, one should use lower temperature, shorter reaction times and CO:H2 ratios wherein excess H2 is avoided. In contrast, if ethanol is the desired product, higher temperatures, longer reaction times and higher H2:CO ratios to provide excess hydrogen are desirable so that acetaldehyde is reduced. Preferred conditions for acetaldehyde formation are temperatures of from 140 to 200°C, an H2:CO ratio from about 0.5:1 to 1:1 and reaction times of from 1 to 3 hours, whereas preferred ethanol reaction conditions are temperatures of from 200 to 220°C, H2:CO ratios of from 1.3 to 1 to 3:1 and reaction times of from 3 to 10 hours. The very high selectivities achievable for ethanol indicates that ethanol formation can be achieved without substantial by-product formation.
- The process of the invention is further illustrated in the following examples.
- HRuCo3(CO)12 and its salts are prepared according to methods described in J. Chem. Soc. (A):1444 (1968). PPNCoRu3 (CO)13 was prepared by the reaction of PPNCo(CO)4 and Ru3 (CO)12 (PPN =Ø3PNPØ3⊕).
- The preparation of CpRu(PØ3)2Co(CO)4 is described as follows. TlCo(CO)4 and CpRu(PØ3)2Cl were prepared by known methods (J. Organomet. Chem., 43:C44 (1972); Aust. J. Chem., 30:1601 (1977)). A mixture of 1.88 g (5 mmoles) TlCo(CO)4 and 3.63 g (5 mmoles) CpRu(PØ3)2Cl in 75 ml THF was refluxed for 18 hours under nitrogen. The cooled solution was filtered to remove the T1C1 which precipitated (1.16 g) and the deep colored filtrate was added to 200 ml pentane and the solution chilled to -20°C overnight. The deep purple crystals which formed were collected on a filter and dried under nitrogen. Yield 1.2 g (28%).
- Analysis. Calculated for C45H30P2O4CoRu, C, 62.74; H, 4.10; P, 7.19; Co, 6.84; Ru, 11.73. Found:
- C, 62.79; H, 4.30; P, 6.98; Co, 6.55; Ru, 11.44.
- The homologation of methanol to ethanol is described in this example. The reaction parameters are 0.86 g of the complex of Example 1, reaction temperature = 220°C; H2:C0 = 1.5; pressure = 27 MPa; CH3I: metal = 2; methanol:metal = 4400 and residence time = 6 hours. The reaction was carried out as follows.
- The high pressure reaction (27 MPa) was carried out in an Autoclave Engineers 1 liter stirred autoclave which was equipped with a catalyst blowcase and which was directly fed by high pressure syn-gas lines. The auto- calve was charged with 250 ml methanol with 50 ml toluene as an internal standard and the appropriate amount of methyl iodide, and preheated to the reaction temperature. The catalyst dissolved in 100 ml methanol was then introduced through the blowcase and the pressure immediately brought to the desired level. Liquid samples were taken at desired intervals during the reaction and a gas sample was taken at the conclusion of the reaction.
- Gas and liquid products were analyzed by gas chromatography using a Perkin-Elmer model 900 or Hewlett Packard Model 5840A instrument. Columns packed with Chromoscrb 102 or Carbowax 20M on Gas Chrom Q were used with temperature programming. Peaks were identified by comparison of known compounds on two different columns if possible. For peaks which could not be identified in this manner, identification was made by gas-chromatograph- mas spectroscopy.
- Quantitative measures were made usinq toluene as an internal standard. Response factors were either determined experimentally or were taken from the compilation of Dietz (J. Gas Chrom., 5:68 (1967)).
-
- As can be seen from the data, high selectivities to ethanol can be achieved using a ruthenium-cobalt complex.
- This example is directed to a comparison of Co complexes, Ru complexes and mixtures thereof versus the preformed Ru-Co complex with respect to the homologation reaction. Example 2 was repeated except that the active metal of the catalyst system was varied. Table II summarizes the results.
-
- Six-hour residence time, 220°C, 27 MPa, 40/60 CO/H2, CH3I/metal ratio = 2, methanol/metal ratio = 4400.
- These data show that either CpRu (PØ3)2Co (CO)4 or mixtures of CpRu(PØ3)2Cl plus C02(CO)8 provide about the same methanol conversions and ethanol product selectivities. Both the preformed complex and the above-cited mixture have a substantial advantage over the individual metal components. The Co and Ru complex mixture is unexpectedly superior as compared to the expected additive effects of the individual metal complexes.
- Fig. 1 illustrates ethanol product selectivity as a function of reaction time. The figure indicates that at 220°C, maximum selectivity to ethanol occurs at from about 3 to 6 hours.
- The effect of temperature, phosphine ligand and metal is illustrated in this example. The procedure of Example 2 was followed except that the residence time was 3 hours and the nature of the metal component of the catalyst system was varied. The data are shown in Table III.
-
- By comparing Examples A and B in Table III, it is seen that lower temperatures favor acetaldehyde formation over ethanol. A reduction of the CO:H2 ratio to 1:1 would further increase the selectivity to acetaldehyde. The importance of the phosphine ligand is demonstrated by comparing Examples A and C. Only a 7% methanol conversion is achieved when Ru(acac)3 is substituted for CpRu(PØ3)2Cl. Finally, the substitution of Rh for Co produces a catalyst system which is virtually inactive for methanol homologation (Examples A and F) under these conditions.
- According to U.S. Patent No. 4,133,966, paragraph bridging columns 4 and 5, most cobalt sources for the production of ethanol for methanol, carbon monoxide, and hydrogen have the disadvantage of producing a variety of alcohols and their derivatives, and do not optimize the formation of ethanol. In contrast, the cobalt- containing catalyst system of the present invention achieves comparable or better selectivities to those shown in U.S. Patent No. 4,133,966. Under present conditions and catalyst systems where ethanol selectivity is low, acetaldehyde selectivity is high, and no change in the catalyst system is required as is indicated by comparing U.S. Patents 4,133,966 and 4,J5] 208. These results and comparisons are set forth below.
-
- A comparison of the results of Table IV with Example VI in U.S. Patent No. 4,133,966 shows that other cobalt sources can achieve ethanol selectivities comparable to or better than cobalt acetylacetonate. In Experiments C. and E. of Table IV, selectivities to ethanol were low, but acetaldehyde selectivities were correspondingly high, and an increase in temperature to 200°C would favor ethanol formation with these particular catalysts. It is noted that under more favorable experimental conditions, the catalyst system of the present invention can achieve ethanol selectivities of about 80-90% (of Tables and II herein).
- In order to achieve improved conversions at elevated temperatures (220°C), CH3I was substituted for I2 as a promoter. When I2 is used at the higher temperatures, no significant improvement in conversion occurs and CH4 becomes a significant impuritv forming in amounts of about 5-10% based on the reacted methanol. At 175°C under the experimental conditions for Table IV, CH31 increases methanol conversion but also results in increased acetaldehyde formation and decreased ethanol formation.
Claims (10)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/098,981 US4348541A (en) | 1979-11-30 | 1979-11-30 | Methanol homologation using cobalt-ruthenium catalysts |
US98981 | 1987-09-21 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0030434A1 true EP0030434A1 (en) | 1981-06-17 |
EP0030434B1 EP0030434B1 (en) | 1984-01-25 |
Family
ID=22271834
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19800304289 Expired EP0030434B1 (en) | 1979-11-30 | 1980-11-28 | Methanol homologation using cobalt-ruthenium catalysts |
Country Status (8)
Country | Link |
---|---|
US (1) | US4348541A (en) |
EP (1) | EP0030434B1 (en) |
JP (1) | JPS5690027A (en) |
AU (1) | AU538457B2 (en) |
BR (1) | BR8007800A (en) |
CA (1) | CA1143748A (en) |
DE (1) | DE3066321D1 (en) |
ZA (1) | ZA807449B (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2495607A1 (en) * | 1980-12-05 | 1982-06-11 | Union Rheinische Braunkohlen | PROCESS FOR THE PREPARATION OF ACETALDEHYDE AND ETHANOL |
EP0084833A2 (en) * | 1982-01-21 | 1983-08-03 | Ruhrchemie Aktiengesellschaft | Process for the production of ethanol and propanol from methanol and synthesis gas |
US4701434A (en) * | 1983-09-09 | 1987-10-20 | Berol Kemi Ab | Promoted nickel and/or cobalt catalyst, its use, and process performed in its presesnce |
EP0305829A2 (en) * | 1987-08-29 | 1989-03-08 | Hoechst Aktiengesellschaft | Process for the preparation of ethanol in admixture with propanol and butenol |
US4863890A (en) * | 1983-09-09 | 1989-09-05 | Berol Kemi Ab | Process for preparing a ruthenium-promoted, halogen-containing nickel and/or cobalt catalyst and a catalyst prepared by the process |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4433176A (en) * | 1982-02-01 | 1984-02-21 | Texaco Inc. | Process for preparing acetaldehyde from methanol and synthesis gas using a novel catalyst composition |
US4433178A (en) * | 1982-02-01 | 1984-02-21 | Texaco, Inc. | Process for preparing acetaldehyde from methanol and synthesis gas using a novel catalyst composition |
US4433177A (en) * | 1982-02-01 | 1984-02-21 | Texaco Inc. | Process for preparing acetaldehyde from methanol and synthesis gas using a novel catalyst composition |
US4389532A (en) * | 1982-05-10 | 1983-06-21 | Eastman Kodak Company | Process for the preparation of acetaldehyde |
JPS60136525A (en) * | 1983-12-26 | 1985-07-20 | Agency Of Ind Science & Technol | Production of ethanol |
JPS60215640A (en) * | 1984-04-10 | 1985-10-29 | Agency Of Ind Science & Technol | Production of ethanol |
US4628121A (en) * | 1985-09-27 | 1986-12-09 | The Halcon Sd Group, Inc. | Preparation of acetaldehyde |
US4954665A (en) * | 1985-11-07 | 1990-09-04 | Union Carbide Chemicals And Plastics Company Inc. | Methanol homologation |
US9040757B2 (en) | 2013-03-08 | 2015-05-26 | Pioneer Energy | Synthesis of high caloric fuels and chemicals |
US9080119B2 (en) | 2011-11-10 | 2015-07-14 | Pioneer Energy | Synthesis of high caloric fuels and chemicals including pentanol from coal, natural gas, and biomass |
US9611186B2 (en) | 2011-11-10 | 2017-04-04 | Pioneer Energy | Synthesis of high caloric fuels and chemicals via ketene and diketene intermediates |
DE102013106790A1 (en) * | 2013-06-28 | 2014-12-31 | Oxea Gmbh | Process for the preparation of 1,3-butanediol |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2007652A (en) * | 1977-11-10 | 1979-05-23 | Chem Systems | Process for the preparation of beta-phenylethyl alcohol |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3248432A (en) * | 1961-12-12 | 1966-04-26 | Commercial Solvents Corp | Process for the production of ethyl alcohol |
US3356734A (en) * | 1963-02-28 | 1967-12-05 | Kuraishi Michio | Process for the production of acetaldehyde |
US3285948A (en) * | 1965-01-22 | 1966-11-15 | Commercial Solvents Corp | Halides of ruthenium and osmium in conjunction with cobalt and iodine in the production of ethanol from methanol |
US4150246A (en) * | 1976-08-30 | 1979-04-17 | Celanese Corporation | Homologation of alkanols |
US4151208A (en) * | 1977-12-23 | 1979-04-24 | Gulf Research & Development Company | Process for the selective preparation of acetaldehyde from methanol and synthesis gas |
US4133966A (en) * | 1977-12-23 | 1979-01-09 | Gulf Research & Development Company | Selective formation of ethanol from methanol, hydrogen and carbon monoxide |
US4171461A (en) * | 1978-09-01 | 1979-10-16 | Air Products And Chemicals, Inc. | Synthesis of ethanol by homologation of methanol |
EP0013464A1 (en) * | 1979-01-09 | 1980-07-23 | Gulf Research & Development Company | Selective formation of ethanol from methanol, hydrogen and carbon monoxide |
US4239924A (en) * | 1979-05-25 | 1980-12-16 | Gulf Research & Development Company | Ethanol from methanol |
FR2458528A1 (en) * | 1979-06-07 | 1981-01-02 | Rhone Poulenc Ind | METHOD FOR APPROVING METHANOL |
FR2460284A1 (en) * | 1979-07-04 | 1981-01-23 | Rhone Poulenc Ind | PROCESS FOR PREPARING ACETALDEHYDE |
US4233466A (en) * | 1979-11-15 | 1980-11-11 | Union Carbide Corporation | Homologation process for the production of ethanol from methanol |
NZ195586A (en) * | 1979-11-27 | 1983-07-29 | British Petroleum Co | Catalytic preparation of ethanol and/or acetaldehyde from synthesis gas |
US4253987A (en) * | 1980-04-10 | 1981-03-03 | Union Carbide Corporation | Homologation process for the production of ethanol from methanol |
-
1979
- 1979-11-30 US US06/098,981 patent/US4348541A/en not_active Expired - Lifetime
-
1980
- 1980-09-17 CA CA000360411A patent/CA1143748A/en not_active Expired
- 1980-11-28 ZA ZA00807449A patent/ZA807449B/en unknown
- 1980-11-28 AU AU64909/80A patent/AU538457B2/en not_active Ceased
- 1980-11-28 JP JP16792780A patent/JPS5690027A/en active Pending
- 1980-11-28 BR BR8007800A patent/BR8007800A/en unknown
- 1980-11-28 DE DE8080304289T patent/DE3066321D1/en not_active Expired
- 1980-11-28 EP EP19800304289 patent/EP0030434B1/en not_active Expired
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2007652A (en) * | 1977-11-10 | 1979-05-23 | Chem Systems | Process for the preparation of beta-phenylethyl alcohol |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2495607A1 (en) * | 1980-12-05 | 1982-06-11 | Union Rheinische Braunkohlen | PROCESS FOR THE PREPARATION OF ACETALDEHYDE AND ETHANOL |
EP0084833A2 (en) * | 1982-01-21 | 1983-08-03 | Ruhrchemie Aktiengesellschaft | Process for the production of ethanol and propanol from methanol and synthesis gas |
EP0084833A3 (en) * | 1982-01-21 | 1983-11-23 | Ruhrchemie Aktiengesellschaft | Process for the production of ethanol and propanol from methanol and synthesis gas |
US4701434A (en) * | 1983-09-09 | 1987-10-20 | Berol Kemi Ab | Promoted nickel and/or cobalt catalyst, its use, and process performed in its presesnce |
US4855505A (en) * | 1983-09-09 | 1989-08-08 | Berol Kemi Ab | Promoted nickel and/or cobalt catalyst, its use, and process performed in its presence |
US4863890A (en) * | 1983-09-09 | 1989-09-05 | Berol Kemi Ab | Process for preparing a ruthenium-promoted, halogen-containing nickel and/or cobalt catalyst and a catalyst prepared by the process |
US4992587A (en) * | 1983-09-09 | 1991-02-12 | Berol Kemi Ab | Process of using a ruthenium-promoted, halogen-containing, nickel and/or cobalt catalyst, to catalyze an amination reaction |
EP0305829A2 (en) * | 1987-08-29 | 1989-03-08 | Hoechst Aktiengesellschaft | Process for the preparation of ethanol in admixture with propanol and butenol |
EP0305829A3 (en) * | 1987-08-29 | 1990-05-02 | Hoechst Aktiengesellschaft | Process for the preparation of ethanol in admixture with propanol and butenol |
Also Published As
Publication number | Publication date |
---|---|
AU6490980A (en) | 1981-06-04 |
CA1143748A (en) | 1983-03-29 |
BR8007800A (en) | 1981-06-16 |
AU538457B2 (en) | 1984-08-16 |
DE3066321D1 (en) | 1984-03-01 |
ZA807449B (en) | 1981-11-25 |
EP0030434B1 (en) | 1984-01-25 |
US4348541A (en) | 1982-09-07 |
JPS5690027A (en) | 1981-07-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0030434B1 (en) | Methanol homologation using cobalt-ruthenium catalysts | |
US4133966A (en) | Selective formation of ethanol from methanol, hydrogen and carbon monoxide | |
US4262154A (en) | Process for the production of ethanol and/or acetaldehyde by reacting methanol with synthesis gas | |
Evans et al. | Regioselective rhodium-catalyzed allylic alkylation with a modified Wilkinson's catalyst | |
US4328375A (en) | Process for the production of ethanol and/or acetaldehyde in the presence of metal complex catalyst systems | |
EP0046680B1 (en) | Improved catalytic hydrogenation of glycolaldehyde to produce ethylene glycol | |
JPS5932454B2 (en) | Method for producing glycol monoalkyl ether and dialkyl ether | |
US4239924A (en) | Ethanol from methanol | |
JPS6332342B2 (en) | ||
EP0108847A1 (en) | Production of acetic acid, propionic acid and their esters | |
US4193943A (en) | Hydroformylation catalysts | |
US4138420A (en) | Hydroformylation catalysts | |
EP0027000B1 (en) | Methanol conversion with co or co+h2 using iron-cobalt catalyst | |
CA1178974A (en) | Alkanols from synthesis gas | |
US4332915A (en) | Production of alkanols from synthesis gas | |
EP0055887A2 (en) | Novel catalyst system and process for producing ethanol using said novel catalyst system | |
EP0013464A1 (en) | Selective formation of ethanol from methanol, hydrogen and carbon monoxide | |
US4278819A (en) | Process for the production of acetaldehyde dimethyl acetal | |
US4357480A (en) | Process for the production of ethanol by the liquid phase hydrocarbonylation of methanol | |
JPS63156739A (en) | Manufacture of carbonyl compound | |
GB2100726A (en) | Manufacture of alkanols from sythesis gas | |
US4259530A (en) | Process for the production of aldehydes by hydroformylation | |
GB2089790A (en) | Preparation of ethylene glycol and ethers thereof | |
EP0649851A1 (en) | Process for preparation of hydridocarbonyltris (triorganophosphorus) rhodium compound | |
CA1107765A (en) | Selective formation of ethanol from methanol, hydrogen and carbon monoxide |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Designated state(s): BE DE FR GB IT NL |
|
17P | Request for examination filed |
Effective date: 19811030 |
|
ITF | It: translation for a ep patent filed |
Owner name: ING. C. GREGORJ S.P.A. |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Designated state(s): BE DE FR GB IT NL |
|
REF | Corresponds to: |
Ref document number: 3066321 Country of ref document: DE Date of ref document: 19840301 |
|
ET | Fr: translation filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19841231 Year of fee payment: 5 |
|
26N | No opposition filed | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19850731 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19850801 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19871130 Year of fee payment: 8 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19881128 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Effective date: 19881130 |
|
BERE | Be: lapsed |
Owner name: EXXON RESEARCH AND ENGINEERING CY Effective date: 19881130 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19890601 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee | ||
GBPC | Gb: european patent ceased through non-payment of renewal fee |